Sonochemical decomposition of organic acids in aqueous solution: understanding of molecular behavior during cavitation by the analysis of a heterogeneous reaction kinetics model

The sonochemical decomposition of a low concentration of butyric acid was performed in an aqueous solution by use of 200kHz ultrasound to discuss the reaction kinetics and molecular behavior during cavitation. Taking into account a Langmuir-type adsorption model, we propose a heterogeneous reaction kinetics model, which is based on the local reaction zone at the interface region of the cavitation bubbles, where the adsorption and desorption of butyric acid molecules from the bulk solution occur during bubble oscillation and then the existing molecules inside the local reaction zone are finally decomposed. To confirm our proposed kinetics model, the rates of decomposition were investigated as a function of the initial concentration of butyric acids in the different pH solutions. It was confirmed that our model could be reasonably applied to explain the obtained results and the pseudo rate constant (k) and the equilibrium constant (K) were able to be calculated: k is 8.0muMmin(-1) (pH 2) and 3.5muMmin(-1) (pH 10), and K is 5.7x10(-3)muM(-1) (pH 2) and 8.0x10(-3)muM(-1) (pH 10), respectively. By the analysis of the obtained K values, it was clear that the ionized organic acid molecules are relatively difficult to accumulate at the reaction zone, because of their lower hydrophobicity compared with that of the neutral ones. The results obtained in the sonochemical decomposition of benzoic acid were also able to be analyzed with the proposed kinetics model. In addition, we proposed an opinion toward the interpretation of a Langmuir-type adsorption model which has often been applied to explain heterogeneous reaction systems.     

A new empirical rate equation for adsorption kinetics at solid/solution interface

It has been shown that most of the previously reported empirical rate equations for kinetics of adsorption at the solid/solution interface show high relative errors at the initial times of adsorption. In the present work we made a modification onto pseudo-first-order and pseudo-second-order models and presented a new empirical rate equation, called the modified pseudo-n-order (MPnO) model. The results of fitting to the experimental data show that the MPnO model has low relative errors in the whole range of adsorption time.     

Adsorptive removal of congo red dye from aqueous solution using bael shell carbon

This study investigates the potential use of bael shell carbon (BSC) as an adsorbent for the removal of congo red (CR) dye from aqueous solution. The effect of various operational parameters such as contact time, temperature, pH, and dye concentration were studied. The adsorption kinetics was modeled by first-order reversible kinetics, pseudo-first-order kinetics, and pseudo-second-order kinetics. The dye uptake process obeyed the pseudo-second-order kinetic expression at pH 5.7, 7 and 8 whereas the pseudo-first-order kinetic model was fitted well at pH 9. Langmuir, Freundlich and Temkin adsorption models were applied to fit adsorption equilibrium data. The best-fitted data was obtained with the Freundlich model. Thermodynamic study showed that adsorption of CR onto BSC was endothermic in nature and favorable with the positive ΔH° value of 13.613 kJ/mol.     

Stochastic Computer Model of the Kinetics of Multicomponent Intercrystalline Adsorption in Solid Solutions

The basic principles of constructing a stochastic computer model of intergranular adsorption kinetics controlled by interatomic pair interactions and the volume diffusion mobility of the components of a solid solution are developed, allowing for the bulk structure of crystals and the equilibrium atomic configuration of intergranular boundaries. The results are presented from computer simulations of the grain boundary segregation of S and P in α-Fe-based alloys.     

Nucleation kinetics in a CuCl solid solution in glass: Calculation and comparison with experiment

The kinetics of formation of CuCl nanoparticles in a glass has been studied. The experimental results obtained have been compared with the results of calculations. A method has been developed for calculating the nucleation kinetics, which decreases the time of calculations by a factor of several tens. This has been achieved using the joint kinetic equation for distributions of clusters over the number of particles and over the radius. The distributions over the number of particles and over the radius have been used for small and large clusters, respectively. The concentration of molecules near the surface of clusters has been determined from the asymptotic solution of the diffusion equation. For subcritical clusters, the concentration of molecules near the cluster surface has been taken to be equal to the average concentration in the solid solution. This method has been used to calculate the nucleation kinetics of CuCl nanoparticles in a glass. The results obtained from the calculation of the time dependences of the increase in the concentration and average radius of clusters agree well with experiment.     

Adsorption kinetics in micellar solutions of nonionic surfactants

Standard models of the adsorption kinetics of surfactants at the air-water surface assume that micelles break down into monomers in the bulk solution and that only monomers adsorb. We show here that micelles of the nonionic surfactant C14E8 adsorb to the surface of a liquid jet at a diffusion-controlled rate. Micellar adsorption can be switched off by incorporation of a small amount of ionic surfactant into the micelle and switched on again by addition of salt. More sophisticated models of adsorption processes in micellar solutions are required that permit a kinetic flux of micelles to the air-water interface.     

Application of the statistical rate theory of interfacial transport to investigate the kinetics of divalent metal ion adsorption onto the energetically heterogeneous surfaces of oxides and activated carbons

Divalent metal cation adsorption from solution onto oxides or activated carbons can be described by the Surface Complexation Model (SCM). We assumed that the adsorbent surface is strongly energetically heterogeneous and derived the adsorption isotherm using rectangular distribution of adsorption energy and condensation approximation for the local isotherm equation. Assuming additionally that the bulk concentration of divalent metal ion is low and does not change considerably during the adsorption process and next applying the Statistical Rate Theory of Interfacial Transport (SRT) we derived the Elovich equation—the experimental formula describing adsorption kinetics.     

Removal of Brilliant Green from wastewater using conventional and ultrasonically prepared poly(acrylic acid) hydrogel loaded with kaolin clay: A comparative study

The present work deals with the removal of Brilliant Green dye from wastewater using a poly(acrylic acid) hydrogel composite (PAA-K hydrogel) prepared by incorporation of kaoline clay. The composite has been synthesized using ultrasound assisted polymerization process as well as the conventional process, with an objective of showing the better effectiveness of ultrasound assisted synthesis. It has been observed that the hydrogel prepared by ultrasound assisted polymerization process showed better results. The optimum conditions for the removal of dye are pH of 7, temperature of 35 °C, initial dye concentration of 30 mg/L and hydrogel loading of 1 g. The extent of removal of dye increased with an increase in the contact time and initial dye concentration. A pseudo-second-order kinetic model has been developed to explain the adsorption kinetics of dye on the PAA-K hydrogel. Thermodynamic and kinetic parameters indicate that the adsorption process is spontaneous in nature and the PAA-K hydrogel prepared by ultrasound process is a promising adsorbent compared to conventional process. The obtained adsorption data has also been fitted into commonly used adsorption isotherms and it has been found that Freundlich as well as Langmuir adsorption isotherm models fits well to the experimental results.     

A comparative study on the effect of hydrodynamic interactions in the non-sequential deposition of concentrated colloidal dispersions: stochastic rotation dynamics and Brownian dynamics simulations

Irreversible adsorption of particles onto a flat surface as a consequence of sedimentation colloidal suspension has been studied by two simulation techniques: Brownian dynamics (BD) and stochastic rotation dynamics (SRD). The purpose of using both methods is to investigate the effect of hydrodynamic interactions on adsorption kinetics and structure of the first monolayer of sediment obtained from the sedimentation of a concentrated and monodisperse colloidal suspension. Three systems were studied, characterised by the Péclet numbers: 0.1, 1.0 and 10. To physically understand the kinetic behaviour, simulation results were analysed using a kinetic model based on chemical reactions. High values of jamming limit (θ_∞ > 0.61) were obtained for both simulation techniques, with the SRD showing the highest figures (0.631) due to the hydrodynamics effect that takes into account the fluid backflow produced on particle sedimentation. A two-step adsorption mechanism was proposed based on the observed kinetic behaviour.     

Adsorption equilibrium and kinetics of dibenzothiophene from n-octane on bamboo charcoal

The adsorption of the model sulfur compound dibenzothiophene (DBT) from n-octane solution on to bamboo charcoal (BC) was investigated. The equilibrium and kinetics of DBT adsorption on BC were examined. Adsorption isotherm of DBT on BC was determined and correlated with two well-known isotherm equations (Langmuir and Freundlich). The equilibrium data for DBT adsorption fitted the Freundlich model well. Two simplified kinetic models including pseudo first-order and pseudo second-order equations were selected to follow the adsorption processes. The adsorption of DBT on BC can be best described by a pseudo second-order equation. The parameters of this best-fit kinetic model were calculated and discussed.     

重新审视桥式吸附甲酸根在铂电极上电催化氧化甲酸过程中的作用 (cited: 2)

基于以前报道的电化学原位ATR-FTIRS数据(Langmuir 22,10399 (2006)和Angewa. Chem. Int. Ed., 50,1159 (2011)),详细讨论了甲酸在铂电极上电催化氧化机理及动力学过程．提出了直接反应路径的动力学模型,即甲酸吸附(同时C-H键活化)作为此反应的决速步骤,此反应路径贡献甲酸氧化反应的大部分电流．该动力学模型可以很好地拟合在无CO毒化影响和浓度在0.1 mol/L以下的红外光谱结果．这种机理预测了甲酸氧化直接途径可能只需要一个Pt原子作为反应位点,甲酸根阻碍活性位点,并非为反应中间物．另外还详细检验了之前其他小组曾提出的甲酸根途径(一级或二级反应)为甲酸氧化直接途径,并指出了引起分歧的原因．     

New method for determination of equilibrium/kinetic sorption parameters

We proposed a new method from which kinetic sorption parameters can be estimated using aqueous phase concentration versus time data commonly available from adsorption tests. The method relies on the analytical solution that was solved for two-site reversible sorption kinetics based on mass conservation law for solute in a batch reaction system. In order to validate the method, model parameters were compared with those of three-stage kinetic models available in the literature. It was revealed that model parameters of the two-site kinetics could accurately be estimated as much as other model parameters. Advantage of the new method is acquisition of additional parameter, distribution or partitioning coefficient (K_d) frequently used in the analysis of chemical transfer in the solid–liquid interface.     

Cr(VI) adsorption mechanism on rice husk ash burned at low temperature by method of IR spectra

Boehm titration method was used to analyze functional groups on cell surface of rice husk ash burned at low temperature in the present paper. Effects of initial pH value and temperature on Cr(VI) adsorption were studied, adsorption capacity was tested with the help of kinetic models and adsorption isotherms, instruments of Fourier transform infrared spectroscopy(FTIR) and scanning electron microscope (SEM) were used to check characteristics and adsorption mechanism of Cr(VI). The results indicated that optimal removing rate was achieved at initial pH value 5, and pH values of aqueous solution changed little be fore and after adsorption process. The adsorbent of rice husk ash could remove Cr(VI) effectively, and the maximum removing rate could be 95% with Cr(VI) concentration 20 mg x L(-1) and achieve 1-2 level of state standard(GB8978-1996). The adsorption process fits pseudo-second-order kinetic model and Langmuir isotherm better, the maximum adsorption capacity of Cr(VI) was 3.2776 mg x g(-1). Results of FTIR showed that amide II band, Si--O--Si, O--Si--O were important for Cr(VI) removal. SEM micrographs revealed that series of needle-shaped precipitation appeared on cell surface, and inorganic precipitation mechanism and redox mechanism might work in the test. As a kind of low cost adsorbent, rice husk ash can be applied to remove heavy metals in environment with great potential.     

Development of long-life-cycle tablet ceramic adsorbent for geosmin removal from water solution

In this study, the tablet ceramic adsorbent (TCA), a silica/iron(III) oxide composite material, has been developed for geosmin (GSM) removal from the water solution. The physicochemical characteristics of TCA were examined with XRD, SEM, EDX and BET analyses. The sorption characteristics of GSM on TCA were investigated in a batch system. Attempts have been made to understand the adsorption kinetics, the effect of initial GSM concentration, solution pH, and reaction time.The batch experiments equilibrium data were well fitted to the Lagergren kinetic equation, which indicate the first-order nature adsorption. Over 82% of the GSM was removed by the TCA within 600 min at an initial concentration of 200 ng/L with 20 g/L of TCA dose. The batch and regeneration study indicated that the TCA is a cost-effective GSM adsorbent with sufficient mechanical strength to retain its physical integrity after long-time adsorption, and high regeneration performance for long-life-cycle application. Almost no second contamination (toxic sludge or leached iron) was observed after adsorption, and the gas resultant of thermal regeneration is harmless to atmospheric environment.     

Adsorption behavior of a textile dye of Reactive Blue 19 from aqueous solutions onto modified bentonite

The aim of this study is to evaluate adsorption kinetics, isotherms and thermodynamic parameters of Reactive Blue 19 (RB19) onto modified bentonite from aqueous solutions. The effects of pH, contact time, initial dye concentration and temperature were investigated in the experimentally. Natural bentonite was modified by using 1,6-diamino hexane (DAH) as a modifying agent. The characterization of modified bentonite (DAH-bentonite) was accomplished by using FTIR, TGA, BET and elemental analysis techniques. The optimum pH value for the adsorption experiments was found to be 1.5 and all the experiments were carried out at this pH value. The pseudo-second-order kinetic model agrees very well with the experimental results. Equilibrium data were also fitted well to the Langmuir isotherm model in the studied concentration range of RB19 at 20 °C. The results indicate that DAH-modified bentonite is a suitable adsorbent for the adsorption of textile dyes.     

红外光谱法研究低温焚烧稻壳灰对Cr(Ⅵ)的吸附机理

采用Boehm滴定法量化了低温焚烧稻壳灰表面官能团,考察了溶液初始pH值和温度对吸附效能的影响,借助动力学方程和吸附等温线,研究了稻壳灰对Cr(Ⅵ)的吸附性能,利用红外图谱、扫描电镜表征了稻壳灰的表面形貌和吸附机理。结果表明：在pH值为5时,稻壳灰对Cr(Ⅵ)取得最优去除效果,吸附前后溶液pH值变化很小。稻壳灰对Cr(Ⅵ)有较强的去除能力,对于20 mg·L-1的Cr(Ⅵ)溶液,最高去除率能达到95%左右,达到《污水综合排放标准GB8978—1996》1～2级标准。吸附过程能更好地符合准二级反应动力学方程和Langmuir等温线方程,饱和吸附容量可达3.277 6 mg·g-1。红外光谱表明酰胺Ⅱ带、Si—O—Si、O—Si—O等在Cr(Ⅵ)吸附过程中可能有重要贡献。扫描电镜图片表明吸附Cr(Ⅵ)后,稻壳灰表面分布有众多的光亮沉积物,有条带状或不规则点斑出现,推测无机微沉淀和氧化还原机理在吸附过程中起重要作用。稻壳灰是一种价格低廉、有应用潜力的高效吸附剂,可以用于水体重金属污染的治理修复。     

Solid-solution strengthening of intermetallic compounds in the region of anomalous thermal behavior of the deforming stress

Strong solid-solution strengthening of intermetallic materials in the region where the deforming stress increases anomalously with temperature is shown to be caused by the stimulating influence of solution atoms on dislocation locking via the Kear-Wilsdorf mechanism. The dependence of the deforming stress on temperature, solution concentration, strain rate, and other parameters is described in terms of a simple model in which the thermally activated kinetics of cross slip of dislocations is modified by solution atoms. The proposed theory is compared with available experimental data for a (Ni_{1 ? c} Fe_c)₃Ge solid solution.     

Effect of electrostatic interaction on the methylene blue and methyl orange adsorption by the pristine and functionalized carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with cysteamine groups by several percentage of mass as adsorbents, then kinetics adsorption capacity was investigated for methylene blue (MB) and methyl orange (MO) as anionic and cationic dyes adsorbate molecules, respectively. The effect of temperature (from 283 to 303 K), contact time and initial concentration of the MB and MO dyes in a solution (10 to 40 ppm) was considered. The optimal contact time was found to be about 60 min. Some kinetics model such as pseudo-first-order, pseudo-second-order, intra-particle diffusion and the Elovich were tested. The adsorptions of MB dye on the pristine and functionalized MWCNT surfaces were found to be the intra-particle diffusion and the pseudo-second-order kinetic model, respectively and for adsorption of MO dye by the pristine and low functionalized MWCNTs and highly functionalized tubes, found to be the pseudo-second-order and intra-particle diffusion kinetic model, respectively, based on the chi-square statistic (X²) and also high correlation coefficient (R²) values.     

On the role of electron-hole pair excitation in the kinetics of atom recombination at metal surfaces

The dynamics of energy relaxation of the adspecies in exoergic processes at metal surfaces has been modeled by means of the master equation approach. The effect of energy disposal to the solid via electron-hole (e-h) pair excitation on the rate of adatom recombination, has been investigated in the case of a discrete set of vibrational levels of the adspecies. The kinetics is solved, analytically, for two recombination channels and by taking into account two energy dissipation pathways of the adspecies. It is shown that dissipation pathways, characterized by a sizable energy transfer per scattering event, affect the kinetics leading to enhanced recombination rates. The kinetic model has been applied to describe experimental data on H(D)-adatom abstraction and recombination at metal surfaces. The rate coefficient of the process is shown to be proportional to the energy power transferred to the solid, owing to the reaction exothermicity, and correlates to the surface electron density.